Process for manufacturing amino-aldehyde compounds



Patented Sept. 13, 1 932 PATENT OFFICE GEORG KALISOHER, Am: HETNBICHRITTER, or gaaaar gsdt a u ns nrm, nun mass HONOLI), or FRAN KFonto-0Nann-ivmm-rnor nnnnrm, ennivrnny, nssicnons ro GENERAL ANILIN'E'WORKS; rim, or NEW YORK, 1\T. eY., A CORPORATION orpELA- WARE PROCESS son MANUFAoIu'RmG AMiNO-ALDEHYDE co'iurofin ns WVe have found that in aromatic aldehydes of the benzene, naphthaleneand anthracene series containingreplaceable halogen atoms intli'eir -molecule, particularly in ortho position to the aldehyde group, these halogen atoms react in a smooth reaction with acidamides and their mono-aryl derivatives.

The process may be carried a manner that the components are heated together in presence orabsence' of a diluent such as nitrobenzene or amylalcoho-l or cyclohexanol with or without' addition-of a catalyst, such as-copper 'or its salts, in ipres- 1%, 'ence of 'an' acid. binding-agent, such'as sodium acetate, alkali carbonates or similar acting agents.

When using, for instance,;ortho-chloro- ]oenzaldehyde and toluenesulfamide in this "simplest case the reaction runs probably according to the following equation:

new compounds. They correspond probably to'the general formula wherein n is the number 1 0r 2 and X means hydrogen or an aryl residue, R means SO or .CO and phenyl stands for a residue of the benzene'series, aryl means an aromatic residue of the benzene, naphthalene or a'nthracene series, which may contain further substituents, inter alia halogen or a further aldehyde group. Especially valuable are the compounds of 'the Y general formula ary1 OHO wherein n, X and arylhave the aforesaid signification and-1R means ..a-=residue of the out in:

benzene series and the groups stand in an adjacent position to the group. They are solid substances generally of a crystalline structure and soluble in caus- I tic alkali solutions. When treated withja saponifyingagen-t they are transformed into the corresponding aminoaldehydes.

If more than one replaceable halogen atom be present in the molecule of the startingmaterial they can be replaced by the acylam ino residue successively. When using haloare substituted at the nitrogen atom by a mono-aryl residue show the same reactivity.

The sulfonio acid amides, such as toluene sulfamides, toluenesulfanilicle and likewise sulfamide itself are"esp'ecia*lly suitable for the present process. But likewisecarbonl'c acid amides, such as benzzt-midaphthalimidia' and other can bevused'.

The present process is favored by the .presence of further substituents in the molecule of thestartingmaterial, whereby the halogen stems are labilized. For instance nitro groupsin orthoor para-position to the halogen atoms are favorable for a smooth re- 7 action.

The present process, according to which 'aminoaldehyecompounds can be produced in a simple manner which compounds were formerly only obtainable with difliculty, is therefore, of considerable technical importance.

Example 1 A :miX-tu're 'of25. parts 'of fienitro-2 chlo' "o'- 'benzaldehyde, 25 parts of I para toluenesulif 1 amide,"-'20 parts ofpotassiumycarbonate, 02- parts of-copp'er poifvderand 0,3 I of cuprous chloride ishe'ated for about 3" hours at 170-190 while 'st-irr-in-g: Then the yellow ish reaction mass is diluted w-ithwater,

-4. Instead of acting with para-toluenesulf- 11 These acylamino compounds are .saponified boiled 05 and filtrated. The yellowish filtrate containing the potassium salt of the toluenesulfamino compound is acidulated by means of dilute hydrochloric acid. Then the new 5-nitro-2-para-toluenesulfaminobenzaldehyde of the formula:

ran-smO-om separates as a yellow precipitate. It is filtered off and dried. Recrystallized from glacial acetic acid it represents colorless prisms melting at about 181182', soluble in a cold caustic soda solution and a hot solution of sodium carbonate with a yellowish color. The phenylhydrazone crystallizes from glacial acetic acid as yellow needles and melts at about 214l with decomposition.

When carrying out the reaction with addi tion of about 100 to 150 parts of nitrobenzene the reaction mass remains thinly liquid. When the reaction is finished the nitrobenzene is removed by steam distillation.

amide one may use carboxylic acid amides, such as benzamide or phthalimide thus forming in the same manner the 5-nitro-2-benzamino or phthalimino-benzaldehyde.

in the usual manner. The toluenesulfamino compound, for instance, may be heated for about half an hour to 6080 after addition of the sixfold to eightfold quantity of sulfuric acid of 9095% strength. Thee-nitro- 2-aminobenzaldehyde thus formed shows the properties as described in literature (see Chem. Centralbl. 1908, I, 921).

Example 2 A mixture of 15 parts of ortho-chlorobenzaldehyde, 30 parts of para-toluenesulfamide, 15 parts of potassium carbonate, 0,2 parts of copper powder and 0,3 parts of cuprous chloride is heated for about 6 hours at 160 180 while stirring. The yellow reaction mass is diluted with hot water, boiled off and filtrated. By acidulating the yellowish filtrate the new 2-para-toluenesulfamino-benz- "aldehyde of the formula:

NH-SOzOCHa CHO l reciPitateS. It is filtered off and dried. I

crystallizes from alcohol as colorless crystals melting at about 203205.

When heating this compound, for instance,

. for half an hour with about the sixfold quantity of sulfuric acid of 90 strength at 60-7 09 the acid residue is split off and the 2-aminobenzaldehyde is obtained. i

In an analogous manner the para-chlorobenzaldehyde yields the 4-aminobenzaldehyde, its 3-nitro derivative the 4-amino-3- nitrobenzaldehyde, the 2.5-dichloroand the 2. 1.5-trichloro-benzaldehyde the correspondin g arylsulfamino-compounds and by saponification thereof the free aminoaldehydes.

When heating ortho-chlorobenzaldehyde for some hours with para-toluenesulfo-paratoluidide in presence of, for instance, sodium acetate a new compound of the formula:

slop-4113:

is obtained.

By heating it with concentrated sulfuric acid the acid residue is split off and simultaneously ring closure occurs, whereby the G-methylacridine is formed.

Example 3 A mixture of'75 parts of 2.6-dichchloro- V benzaldehyde, 25 parts of para-toluenesulfamide, 22 parts of potassium carbonate, 0,2 parts of copper powder and 0.2 parts of cuprous chloride is heated for about 3 hours at 160180.

Then the reaction mass is diluted with water and the exceeding dichlorobenzaldehyde is expelled by steam-distillation. The remaining yellow solution is filtrated and acidulated, whereby the new 2-toluenesulfamino-6-chlorobenzaldehyde of the formula:

Example 4 20 parts of 3-nitro-2.6-dichlorobenza-ldehyde are mixed with 40 parts of toluenesulfamide, 30 parts of potassium carbonate, 0,2 parts of copper powder, 0,3 parts of cuprous chloride and about 200 parts of nitrobenzene and the mixture is heated to boiling for about {1 hours while stirring. The reaction mass is era-Osm-rrn worked up as describedlin Example 33 The or the corresponding amount of benzenesulf condensation product has been proved as free i from halogen. On account of the anaylsis we ascribe to it the probable formula:

When using vice versa an excess of 3-nitro- 2.6-dichlorobenzaldehyde it is possible to replace only one of the halogen atoms by the toluenesulfamino residue.

Ewample 5 I A mixture of 10 parts of 2.5-CliChlO1O-;'

terephthalaldehyde, 25 parts of para-toluenesulfamide, 18 parts of potassium carbonate,

I 0,2 parts of copper, 0,2 parts of cuprous chloride and about parts of nitrobenzene is heated for about 3 hours to boiling while stirring. In the same manner as described in the foregoing examples the new di-toluenesulfamino compound of the formula: v

and by saponifying this latter compound the new 2.5-diamino-terephthalaldehyde of the w: Jformula is obtained, which crystallizes from for'instance tri-chlorobenzene as yellow needles, melting above 300.

new aldehyde com' amide, 20 partsof potassium carbonate, 0,2 parts of copperand 0,2'pa-rts of cuprous chloride and about 7 5 parts of nitrobenzene and themixture is heated at 200 for about 79 4czh'ours, The nitrobenzene is expelled by steam distillation and the arylsulfaminocompound is isolated as described above;

The new 10-para-toluenesulfan1inoanthracene-9-aldehyd'e corresponding probably to the formula:

w thus obtained crystallizes from glacial acetic acid as weakly yellow needles melting at about 270 with decomposition.

Example 7' 27 parts of l-chloroanthraquinone aldehyde are mixed with 20 parts of para-toluene sulfamide, 2O parts'of anhydrous potassium acetate, 0,5 parts of copper acetate and about 300 parts of amylalcohol and the mixtureis heated for some hours in an apparatus pro vided with a reflux condenser. When cold the alcohol is expelled by steam distillation and the reaction product is purified by dissolving it in water with addition of some caustic soda solution. From the brown solution a weakly yellowish substance is iso lated by acidulation, soluble in concentrated sulfuric acid with a yellowish brown color. After addition of water tothis solution the 1 amino anthraquinone-2aldehyde is ob tained.

It appears from the examples that the replaceable halogen atomsstand in ortho'e or,

when the aldehyde group occupies the 9-po- "sition of the anthracene nucleus, in the 10 position thereof, united by a direct bond with the 9-position, all these positions being defined in'the following claims as adjacent for brevitys sake.

We claim: p

1. The proc'essfor producing amino-arylaldehydes which comprises condensing anaromatic aldehyde containing atleast one replaceable halogen atom in its molecule which stands in adjacent position to'the aldehydegroup with an amido compound of the general formula NH'X--Rphenyl, wherein X 1 means hydrogen or an arylradical, R. stands" 1301 inixed with QO part's'ofpara-toluenesulfamide Lasso, or'CO and phenyl'fo'r a radicalof the benzene series and saponifying the acylaminoaldehyde compound thus formed.

2. The process for producing amino-arylaldehydes which comprises condensing an aromatic aldehyde containing at least one replaceable halogen atom in its molecule which stands in adjacent position to the aldehyde groupjwith an amido compound-of the general formula NHXRphenyl, wherein X zmeans hydrogen, or an aryl radical,R stands for S or CO and phenyl for a radical of the benzene series in presence of a diluent and saponifying the acylaminoaldehyde compound thus formed. 7

3. The process'for producing amino-arylaldehydes which comprises condensing an aromatic aldehyde containing at least one replaceable halogen atom in its molecule which stands in adjacent position to the aldehyde fifligroup with an amido compound of the general formula NHXR-phenyl, wherein X means hydrogen, or an aryl radical, R stands for S0 or CO and phenyl for a radical of the benzene series in presence of a diluent 2 ;;and with addition of a catalyst, and saponifying the acylaminoaldehyde compound thus formed.

4. The process for producing amino-arylaldehydes which comprises condensing an 39, :aromatic aldehyde containing at least one replaceable halogen atom in its molecule which stands in adjacent position to the aldehyde group with an arylsulfamido compound and saponifying the acylaminoaldehyde com- 3Jipound thus formed.

5. The process for producing amino-arylaldehydes which comprises condensing an aromatic aldehyde containing at least one replaceable halogen atom in its molecule which .0.;l'stands in adjacent position to the aldehyde group with an arylsulfamido compound in presence of a diluent and saponifying the acylaminoaldehyde compound thus formed.

6. The process for producing amino-aryl- .11aldehydes which comprises condensing an aromatic aldehyde, containing at least one replaceable halogen atom in its molecule which stands in adjacent position to the aldehyde group with an arylsulfamido compound Q in presence of adiluent and with additionof a catalyst, andsaponifying the acylaminoaldehyde compound thus formed.

7. The process for producing amino-arylaldehydes which comprises condensing an lizlaromatic aldehyde containing at least one replaceable halogen atom in its molecule which stands in adjacent position to the aldehyde group with an arylsulfamide in presence of a diluent and with addition of a catalyst, and ."saponifying the acylaminoaldehyde compound thus formed. 1

'8. The process for producing new acylamino-aldehyde compounds which comprises condensing an aromatic aldehyde containing at least one replaceable halogen atom in its molecule which stands in adjacent position to the aldehyde group with an amido compound of the general formula NHXR phenyl, wherein X means hydrogen, or an aryl radical, R stands for S02 or CO and phenyl for a radical of the benzene series in presence of diluent and with addition of a catalyst.

9. As new compounds aromatic acylaminoaldehyde compounds corresponding probably to the general formula tion to the aldehyde group with an aryl sul-.-

famido compound in presence of a diluent and with addition of a catalyst.

11. As new compounds armomatic arylsulfaminoaldehyde compounds corresponding probably to the general formula:

W1 ::1XOSO2R)n wherein n is the number 1 or 2, X means hydrogen or an aryl group, R means a radical of the benzene series and aryl means an aromatic radical of the benzene-, naphthaleneor anthracene series the group NHSO R standing in an adjacent position to the CH0 group, which compounds are solid substances generally of a crystalline structure acid, soluble in caustic alkali solutions.

12. The process for producing new acylamino-compounds which comprises condensing an aromatic aldehyde containing at least one replaceable halogen atom in its molecule which stands in adjacent position to the aldehyde group with an arylsulfamide in presence of a diluent and with addition of a catalyst.

13. As new compounds aromatic arylsulfaminaldehyde compounds corresponding probably to the general formula:

' NHS02'R aryl 0H0 wherein R means a radical of the benzene series, aryl means an aromatic radical of the benzene-, naphthaleneor anthracene series the group NHSO R standingin an adjacent position to the CH0 group, which compounds are solid substances generally of a crystalline structure and soluble in caustic alkali solutions.

14. As new compounds aromatic sulfaminaldehyde compounds corresponding probably to the general formula:

NHSOnary1 wherein X and Z means hydrogen or a nitrogroup, Y means hydrogen, chlorine or the group NHSO aryl, which products are solid substances generally of a crystalline structure and soluble in caustic alkali solutions. In testimony whereof, We aflix our signatures.

GEORG KALISCHER. HEINRICH BITTER. ERNST HONOLD. 

